Benzoisothiazoleazobenzmorpholine of tetrahydroquinone compounds

ABSTRACT

Azo compounds, having the formula ##STR1## in which R 1  and R 2  are hydrogen, alkyl, alkoxy or halogen and A is a 2-position substituted tetrahydroquinoline type coupler which may be further substituted, or a benzomorpholine type coupler for disperse azo dyes, produce bright, level reddish-blue to blue shades on synthetic polyamide fiber and exhibit good to excellent fastness to light, sublimation, ozone and gas.

This is a continuation of application Ser. No. 418,639 filed Nov. 23, 1973, now abandoned, which is a continuation-in-part of Ser. No. 252,645 filed May 12, 1972, abandoned.

This invention concerns novel azo compounds consisting of certain benzisothiazole diazo components and tetrahydroquinoline and benzomorpholine coupling components. This invention also concerns synthetic polyamide fibers dyed with the novel azo compounds.

Our novel azo compounds have the general formula ##STR2## in which R¹ and R² each is hydrogen, lower alkyl, lower alkoxy, chlorine and bromine and A is a 1,2,3,4-tetrahydroquinoline or benzomorpholine disperse azo dye coupling component. These azo compounds are particularly useful for dyeing synthetic polyamide fibers reddish-blue to blue shades. In addition to the commercially-desirable blue shades produced by our compounds on polyamide fibers, they exhibit good to excellent fastness and dyeability properties on such fibers. We have found our dyes to possess good fastness to light, gas, ozone, crocking, sublimation and washing and good build-up. This desirable combination of color, fastness properties and dyeability properties distinguishes our novel compounds from those described in the prior art.

The coupler radicals represented by A are well known in the art of disperse azo dyes as evidenced by the great number of U.S. and foreign patents disclosing such radicals. These known coupling components are attached to the azo group by a carbon atom which is a ring member of the benzene moiety of the coupler and which is in a para-position relative to the nitrogen atom of the coupler nucleus.

Typical of the couplers represented by A are those conforming to the formulas ##STR3## in which R³ through R⁹ represent hydrogen or a wide variety of substituents. Examples of the substituents represented by R³ and R⁴ include halogen and unsubstituted and substituted alkyl, alkoxy, alkylthio, arylthio and acylamido radicals. Such acylamido groups include those having the formula --NH--X--R¹⁰ in which X is --CO--, --COO--, or --SO₂ and R¹⁰ is hydrogen, unsubstituted or substituted alkyl, cycloalkyl, or aryl or when X is --CO--, or --SO₂ --, R¹⁰ also can be amino, alkylamino, dialkylamino, arylamino, or furyl. The alkyl groups represented by R¹⁰ preferably are hydrogen, unsubstituted lower alkyl or lower alkyl substituted, for example, with halogen, aryl, cyano, lower alkylsulfonyl, hydroxy, lower alkylthio, lower alkanoyloxy, etc. As used herein to describe a substituent containing an alkyl moiety, "lower" designates a carbon content of one to about four carbon atoms. Cyclohexyl and lower alkylcyclohexyl are representative cycloalkyl groups represented by R¹⁰. Methylamino, ethylamino, and butylamino are typical alkylamino groups which R¹⁰ can represent. Typical aryl groups represented by R¹⁰ and the aryl component of the arylamino groups represented by R¹⁰ are described hereinbelow. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, bromoacetyl, trifluoroacetyl, phenylacetyl, methoxyacetyl, ethylthioacetyl, methylsulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2-cyanoethylsulfonyl, 2-methoxyethylsulfonyl, 2-chloroethylsulfonyl, cyclohexoyl, 4-ethylcyclohexoyl, benzoyl, 4-ethylbenzoyl, 4-cyanobenzoyl, 4-ethoxycarbonylbenzoyl, phenoxycarbonyl, 2,4-dichlorophenoxycarbonyl, 4-bromophenoxycarbonyl, 4-acetamidophenoxycarbonyl, benzenesulfonyl, p-toluenesulfonyl, 4-propionamidophenylsulfonyl, 4-chlorophenylsulfonyl, cyclohexoxycarbonyl, 4-butylcyclohexylsulfonyl, ethylcarbamoyl, butysulfamoyl, phenylcarbamoyl, p-tolylcarbamoyl, p-anisylcarbamoyl, and phenylsulfamoyl are typical groups represented by --X--R¹⁰.

The alkyl and alkoxy groups which can be present on the carbon atoms of the coupler nucleus preferably are unsubstituted lower alkyl and lower alkoxy such as methyl, ethyl, methoxy, ethoxy and butoxy. Phenoxy, p-tolyloxy, p-ethoxyphenoxy, methylthio, ethylthio, butylthio, phenylthio, m-acetamidophenylthio, and p-chlorophenylthio are typical aryloxy, alkylthio and arylthio groups which can be present on the coupler ring. R⁵ preferably is hydrogen or methyl or, when R⁶ and R⁷ each is hydrogen, R⁵ also can be lower alkyl, and R⁶ and R⁷ each is hydrogen or methyl.

R⁸ can represent unsubstituted or substituted alkyl of up to about eight or more carbon atoms or cycloalkyl such as the cycloalkyl groups represented by R¹⁰. The substituents which can be present on alkyl radical R⁸ are limited primarily only by economic considerations and include hydroxy, lower alkoxy, halogen, cyano, succinimido, glutarimido, 1,2,4-triazolylthio, phthalimido, cyclohexyl, aryl, and groups having the formula --NH--X--R¹⁰, --X--R¹⁰, --OCO--R¹⁰, and --OCOO--R¹⁰. Couplers containing such substituents are well known in the art and/or can be prepared by known means. Preferably, the substituted alkyl radicals represented by R⁸ are substituted lower alkyl.

Preferred couplers represented by A are those of formulas (II) and (III) in which

R³ is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, lower alkoxycarbonylamino or lower alkoxyamino;

R⁴ is hydrogen, lower alkyl, lower alkoxy, chlorine or bromine;

R⁵ is hydrogen, lower alkyl or, when R⁶ and R⁷ each is methyl, R⁵ is methyl;

R⁶, R⁷ and R⁹ each is hydrogen or methyl; and

R⁸ is lower alkyl or lower alkyl substituted with hydroxy, formamido, sulfonamido, lower alkylsulfonamido, lower dialkylsulfonamido, hydroxy substituted lower alkanoylamino, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkanoylamino, lower alkoxycarbonylamino, lower alkanoyloxy, or lower alkoxycarbonyl.

A group of our novel compounds which, because of their cost:performance ratio, are especially valuable dyes for synthetic polyamide fibers have the formula ##STR4## wherein

R¹ is hydrogen or a chlorine or bromine atom positioned at the 5 or 6 position;

R³ is methyl, lower alkoxycarbonylamino, lower alkanoylamino or lower alkanoylamino substituted with hydroxy, lower alkoxy or halogen;

R⁵ is hydrogen, lower alkyl or, when R⁶ and R⁷ are methyl, R⁵ is methyl;

R⁶ and R⁷ each is hydrogen or methyl; and

R⁸ is lower alkyl, lower alkyl substituted with formamido, sulfonamido, lower alkylsulfonamido, lower dialkylsulfonamido, hydroxy substituted lower alkanoylamino, hydroxyethyl, hydroxypropyl, lower alkoxyethyl, lower alkoxypropyl, carbamoylethyl, lower alkylcarbamoylethyl, lower alkanoylaminoethyl, lower alkanoylaminopropyl, lower alkoxycarbonylaminoethyl, lower alkoxycarbonylaminopropyl, lower alkylsulfonamidoethyl or lower alkylsulfonamidopropyl.

The azo compounds of the invention are prepared by diazotizing known 3-amino-2,1-benzisothiazoles and coupling the resulting diazonium salt with a tetrahydroquinoline or benzomorpholine disperse dye coupler according to conventional procedures. The couplers are known compounds and/or can be obtained by published procedures or techniques analogous thereto. The novel azo compounds, their use and their preparation are further illustrated by the following examples.

EXAMPLE 1

To 5 ml. of concd. H₂ SO₄ is added 0.72 g. of NaNO₂ portionwise below 80° C. The solution is cooled and 10 ml. of 1:5 acid (1 part propionic: 5 parts acetic acid) is added below 20° C. The mixture is cooled further and 3-amino-2,1-benzisothiazole (1.5 g.) is added, followed by 10 ml. of 1:5 acid, all at 0°-5° C. The diazonium, after stirring at 0°-5° C. for 1 hr., is added to an ice cold solution of N-2-acetamidoethyl-2,7-dimethyl-1,2,3,4-tetrahydroquinoline (2.46 g.) in 15 ml. of 1:5 acid, below 10° C. The pH of the coupling mixture is adjusted to Congo Red with the addition of NH₄ OAc and coupling is allowed 45 min. at 10° C. The coupling mixture is drowned in water and the azo product is collected by filtration, washed with water and air-dried. The azo compound obtained imparts reddish-blue shades to nylon and exhibits good fastness properties.

EXAMPLE 2

3-Amino-5-chloro-2,1-benzisothiazole (1.84 g.) is dissolved in 25 ml. of 85% H₃ PO₄. A portion (0.72 g.) of NaNO₂ is added portionwise below 0° C. to the H₃ PO₄ solution. The diazonium, after stirring at 0° l C. for 2.0 hr., is added to an ice-cold solution of N-ethyl-2,2,4-trimethyl-7-acetamido-1,2,3-4-tetrahydroquinone (2.46 g.) in 15 ml. of 1:5 acid below 10° C. The pH of the coupling mixture is added to Congo Red with the addition of NH₄ OAc and coupling is allowed 1.0 hr. at 10° C. The coupling mixture is drowned in water and the product is collected by filtration, washed with water and air-dried. The azo dye obtained imparts blue shades to nylon.

EXAMPLE 3

A diazonium solution prepared as described in Example 2 is added to a chilled solution of N-ethyl-2,7-dimethylbenzomorpholine (1.91 g.) dissolved in 15 ml. of 1:5 acid. The coupling and isolation techniques described in Example 2 yield an azo compound which produces level, fast, blue shades on nylon fibers.

The compounds set forth in the examples of Tables I and II are prepared by the procedures described hereinabove and conform, respectively, to the formulas ##STR5## The color given for each of the compounds of Tables I and II refers to the shade it produces on nylon 66 fibers. Examples 1 and 2 of Table I and Example 60 of Table II designate the structures of the compounds obtained in the preceding examples.

                                      Table 1                                      __________________________________________________________________________     Example                                                                        No.  R.sup.1, R.sup.2                                                                     R.sup.2, R.sup.4, R.sup.5, R.sup.6, R.sup.7                                                      R.sup.8                                                                              Color                                       __________________________________________________________________________     1    H     2,7-di-CH.sub.3   C.sub.2 H.sub.5     Reddish-blue                  2    5-Cl  2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               C.sub.2 H.sub.5     Blue                          3    H     2-CH.sub.3        C.sub.2 H.sub.5     Reddish-blue                  4    H     2,2,4-tri-CH.sub.3                                                                               CH.sub.2 CH.sub.2 CONH.sub.2                                                                       Violet                        5    H     2-CH.sub.3        CH.sub.2 CH.sub.2 NHCOOC.sub.2 H.sub.5                                                             Violet                        6    H     2,7-di-CH.sub.3   C.sub.2 H.sub.5     Reddish-blue                  7    H     2,7-di-CH.sub.3   CH.sub.2 CH.sub.2 OH                                                                               Reddish-blue                  8    H     2,7-di-CH.sub.3   CH.sub.2 CH(OH)CH.sub.3                                                                            Reddish-blue                  9    H     2,7-di-CH.sub.3   CH.sub.2 CH(OH)CH.sub.2 OCH(CH.sub.3).sub.2                                                        Reddish-blue                  10   H     2,7-di-CH.sub.3   CH.sub.2 CH(OH)CH.sub.2 Cl                                                                         Reddish-blue                  11   H     2,2,4,7-tetra-CH.sub.3                                                                           (CH.sub.2).sub.3 NHCOCH.sub.3                                                                      Reddish-blue                  12   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5                                                                           Reddish-blue                  13   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                  Reddish-blue                  14   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub. 2 CH.sub.2 OC.sub.6 H.sub.5                                                                Reddish-blue                  15   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                        Reddish-blue                  16   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 CONH.sub.2                                                                       Reddish-blue                  17   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                      Reddish-blue                  18   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 CN                                                                               Violet                        19   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                                Violet                        20   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 NHC.sub.2                                                               Violet5                       21   H     2,2,4,7-tetra-CH.sub.2                                                                            ##STR6##           Reddish-blue                  22   H     2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.3 CH.sub.2 NHSO.sub.2 CH.sub.3                                                              Reddish-blue                  23   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OCH.sub.3                                                                        Blue                          24   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OH                                                                               Blue                          25   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               (CH.sub.2).sub.3 NHCOCH.sub.3                                                                      Blue                          26   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 CH(CH.sub.3)CH.sub.3                                                                      Blue                          27   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                               Blue                          28   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               (CH.sub.2 ).sub.3 OH                                                                               Blue                          29   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 CH.sub.2 OOCOC.sub.2 H.sub.5                                                              Blue                          30   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 C.sub.6 H.sub.11                                                                          Blue                          31   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                               CH.sub.2 C.sub.6 H.sub.5                                                                           Blue                          32   H     2,2,4-tri-CH.sub.3 -7-NHCOOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.5     Blue                          33   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.2 OH                                                            C.sub.2 H.sub.5     Blue                          34   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.2 CH.sub.2 OH                                                    ##STR7##           Blue                          35   H     2,2,4-tri-CH.sub.3 -7-NHCOC.sub.6 H.sub.11                                                        ##STR8##           Blue                          36   H     2,2,4-tri-CH.sub.3 -7-NHCOC.sub.6 H.sub.3                                                        C.sub.2 H.sub.5     Blue                          37   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.2 Cl                                                            C.sub.2 H.sub.5     Blue                          38   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.2 OC.sub.6 H.sub.5                                              C.sub.2 H.sub.5     Blue                          39   H     2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.2 C.sub.6 H.sub.5                                               C.sub.2 H.sub.5     Blue                          40   H     2-CH(CH.sub.3).sub.2 -7-NHCOCH.sub.3                                                             CH(C.sub.2 H.sub.5 )(CH.sub.2).sub.4                                           CH.sub.3            Blue                          41   H     2-CH(CH.sub.3).sub.2 -7-NHCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OH                                                                               Blue                          42   5-Cl  2-CH(CH.sub.3).sub.2 -7-NHCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OH                                                                               Blue                          43   5-Cl  2-CH(CH.sub.3).sub.2 -7-NHCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                      Blue                          44   5-Cl  2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 OH                                                                               Blue                          45   5-Cl  2,2,4,7-tetra-CH.sub.3                                                                           (CH.sub.2).sub.3 NHCOCH.sub.3                                                                      Blue                          46   5-Cl  2,2,4,7-tetra-CH.sub.3                                                                           CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                     Blue                          47   5-Br  2-CH.sub.3 -7-NHCOCH.sub.3                                                                       C.sub.2 H.sub.5     Blue                          48   6-Cl  2-CH.sub.3 -7-NHCOCH.sub.3                                                                       C.sub.2 H.sub.5     Blue                          49   6-CH.sub.3                                                                           2-CH.sub.3 -7-NHCOCH.sub.3                                                                       C.sub.2 H.sub.5     Blue                          50   6-OCH.sub.3                                                                          2-CH.sub.3 -7-NHCOCH.sub.3                                                                       CH.sub.2 CH.sub.2 CON(C.sub.2 H.sub.5)                                                             Blue                          51   5-OCH.sub.3                                                                          2-CH.sub.3 -7-NHCOCH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                        Blue                          52   6-OCH.sub.3                                                                          2-CH.sub.3 -7-NHCOCH.sub.3                                                                       C.sub.2 H.sub.5     Blue                          53   5-Cl  2,2,4-tri-CH.sub.3 -7-OCH.sub.3                                                                  CH.sub.2 CH.sub.2 OH                                                                               Blue                          54   5-Cl  2,2,4-tri-CH.sub.3 -5,8-di-OCH.sub.3                                                             CH.sub.2 CH.sub.2 OH                                                                               Blue                          55   5-Cl  2,2,4,5,8-penta-CH.sub. 3                                                                        CH.sub.2 CH.sub.3 OH                                                                               Blue                          56   5-Cl  2,2,4-tri-CH.sub.3 -7-Cl                                                                         C.sub.2 H.sub.5     Reddish-blue                  57   5-Cl  2,2,4,5-tetra-CH.sub.3 -8-OCH.sub.3                                                              C.sub.2 H.sub.5     Blue                          58   5-Cl  2,2,4,8-tetra-CH.sub.3 -5-OCH.sub.3                                                              C.sub.2 H.sub.5     Blue                          59   5,6,-di-Cl                                                                           2,7-di-CH.sub.3   CH.sub.2 CH.sub.2 CONH.sub.2                                                                       Reddish-blue                  __________________________________________________________________________

                                      Table II                                     __________________________________________________________________________     Example                                                                        No.  R, R.sup.2                                                                           R.sup.3, R.sup.4, R.sup.5, R.sup.7, R.sup.9                                               R.sup.8      Color                                       __________________________________________________________________________     60   5-Cl  2,7-di-CH.sub.3                                                                           --C.sub.2 H.sub.5                                                                           Blue                                        61   H     2,7-di-CH.sub.3                                                                           --C.sub.2 H.sub.5                                                                           Blue                                        62   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 OH                                                                      Blue                                        63   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                             Blue                                        64   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 Cl                                                                      Blue                                        65   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 CN                                                                      Blue                                        66   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 CONH.sub.2                                                              Blue                                        67   H     2,3,7-tri-CH.sub.3                                                                        --CH.sub.2 CH.sub.2 CONH.sub.2                                                              Blue                                        68   H     2,3,3,7-tetra-CH.sub.3                                                                    --CH.sub.2 CH.sub.2 CONH.sub.2                                                              Blue                                        69   H     2,3,3,7-tetra-CH.sub.3                                                                    --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        70   H     3,3,7-tri-CH.sub.3                                                                        --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        71   H     3,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        72   H     3-CH(CH.sub.3).sub.2 -7-CH.sub.3                                                          --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        73   H     3-C.sub.2 H.sub.5 -7-CH.sub.3                                                             --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        74   H     2-C.sub.2 H.sub.5 -7-CH.sub.5                                                             --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        75   H     2-C.sub.6 H.sub.5 -7-CH.sub.3                                                             --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        76   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        77   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3                                                     Blue                                        78   H     2,7-di-CH.sub.3                                                                           --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        79   H     2,3,7-tri-CH.sub.3                                                                        --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        80   H     2,3,3,7-tetra-CH.sub.3                                                                    --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        81   H     3,3,7-tri-CH.sub.3                                                                        --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        82   H     3,7-di-CH.sub.3                                                                           --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        83   H     2-C.sub.6 H.sub.5 -7-CH.sub.3                                                             --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        84   H     3-C.sub.2 H.sub.5 -3,7-di-CH.sub.3                                                        --(CH.sub.2).sub.3 NHSO.sub.2 CH.sub.3                                                      Blue                                        85   H     2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 OCH.sub.3                                                               Blue                                        86   H     2,7-di-CH.sub.3                                                                           --XCH.sub.2 CH(OH)CH.sub.3                                                                  Blue                                        87   5-Cl  2,7-di-CH.sub.3                                                                           --C.sub.2 H.sub.5                                                                           Blue                                        88   5-Cl  2,7-di-CH.sub.3                                                                           --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        89   5-Cl  2-CH.sub.3 --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        90   5-Cl  2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        91   5-Cl  2-CH.sub.3 -7-OCH.sub.3                                                                   --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        92   5-Cl  2-CH.sub.3 -7-OCH.sub.3                                                                   --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        93   5-Cl  2,7-di-CH.sub.3                                                                           --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        94   5-Cl  2-CH.sub.3 -7-NHCOCH.sub.3                                                                --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        95   5-Cl  2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        96   5-OCH.sub.3                                                                          2,7-di-CH.sub.3                                                                           --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        97   5-CH.sub.3                                                                           2,7-di-CH.sub.3                                                                           --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        98   5-CH.sub.3                                                                           2-CH.sub.3 -7-NHCOCH.sub.3                                                                --(CH.sub.2).sub.3 NHCOCH.sub.2                                                             Blue                                        99   5-OCH.sub.3                                                                          2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 NHCOOC.sub.2 H.sub.5                                                    Blue                                        100  6-OCH.sub.3                                                                          2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 NHCOOC.sub.2 H.sub.5                                                    Blue                                        101  6-Cl  2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 CONH.sub.2                                                              Blue                                        102  6-CH.sub.3                                                                           2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 CONH.sub.2                                                              Blue                                        103  H     2-CH.sub.3 -7-NHCOCH.sub.3                                                                --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        104  H     2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        105  H     2-CH.sub.3 -7-NHCOCH.sub.3                                                                --CH.sub.2 CH.sub.2 CONH.sub.3                                                              Blue                                        106  H     2-CH.sub.3 -7-OCH.sub.3                                                                   --CH.sub.2 CH.sub.2 CONH.sub.2                                                              Blue                                        107  H     2-CH.sub.3 -7-OCH.sub.3                                                                   --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        108  H     2-CH.sub.3 -7-OCH.sub.3                                                                   --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        109  H     2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        110  H     2-CH.sub.3 --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                            Blue                                        111  H     2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        112  5-OCH.sub.3                                                                          2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        113  5-CH.sub.3                                                                           2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        114  6-Cl  2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        115  6-OCH.sub.3                                                                          2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        116  6-CH.sub.3                                                                           2-CH.sub.3 --(CH.sub.2).sub.3 NHCOCH.sub.3                                                             Blue                                        __________________________________________________________________________

The novel azo compounds can be applied to synthetic polyamide, polyester and cellulose acetate fibers according to known disperse dyeing techiques. Various dispersing and wetting agents can be employed in the dispersion of the finely divided dye compound in an essentially aqueous dyebath. Procedures by which the compounds of the invention can be applied to polyamide textile materials are described in U.S. Pat. Nos. 3,100,134 and 3,320,021. The following example illustrates a method for applying the novel compounds to polyamide fibers.

EXAMPLE 117

The azo compound (16.7 mg.) of Example 2 is dispersed in 10 cc. of 2-methoxyethanol. A smal amount (3-5 cc.) of a 3% sodium lignin sulfonate solution is added, with stirring, and then the volume of the bath is brought to 150 cc. with water. A 5 g. textile fabric made of nylon 66 fibers is placed in the bath and worked 10 minutes without heat. The bath is then slowly brought to the boil over a 30-minute period and the dyeing is carried out at the boil for one hour. The dyed fabric is then removed from the dyebath, rinsed with water and dried in an oven at 250° F. The fabric is dyed a bright shade of blue exhibiting excellent fastness properties when tested in accordance with the procedures described in the Technical Manual of the American Association of Textile Chemists and Colorists, 1968 edition.

Dyes of great interest shown in Table III below have the formula; ##STR9## wherein

R¹ is hydrogen, chlorine, or bromine;

R³ is CH₃, NHCOCH₃, NHCOH;

R⁵ is hydrogen or --CH₃ ; and

R⁸ is --(CH₂) NHCOH where n = 2 or 3.

These dyes have particularly good light fastness, migration, buildup, crock resistance and ozone fastness on nylon fibers, particularly carpets.

                                      TABLE III                                    __________________________________________________________________________     Example No.                                                                           R.sup.1                                                                          R.sup.3  R.sup.5                                                                           R.sup.8     Color on Nylon                                __________________________________________________________________________     118    H CH.sub.3 OCNH                                                                           H  C.sub.2 H.sub.5                                                                            Blue                                          119    H CH.sub.3 OCNH                                                                           H  C.sub.2 H.sub.4 CONH.sub.2                                                                 Blue                                          120    Cl                                                                               CH.sub.3 OCNH                                                                           H  C.sub.2 H.sub.4 CONH.sub.2                                                                 Blue                                          121    Cl                                                                               CH.sub.3 OCNH                                                                           H  C.sub.3 H.sub.6 NHCOH                                                                      Blue                                          122    H CH.sub.3 OCNH                                                                           H  C.sub.2 H.sub.5 NHCOH                                                                      Blue                                          123    Cl                                                                               CH.sub.3 OCNH                                                                           H  C.sub.2 H.sub.5 NHCOH                                                                      Blue                                          124    H CH.sub.3 OCNH                                                                           CH.sub.3                                                                          C.sub.3 H.sub.6 NHCOH                                                                      Blue                                          125    Cl                                                                               CH.sub.3 OCNH                                                                           CH.sub.3                                                                          C.sub.3 H.sub.6 NHCOH                                                                      Blue                                          126    H CH.sub.3 OCNH                                                                           CH.sub.3                                                                          C.sub.2 H.sub.5 NHCOH                                                                      Blue                                          127    Cl                                                                               CH.sub.3 OCNH                                                                           CH.sub.3                                                                          C.sub.2 H.sub.5 NHCOH                                                                      Blue                                          128    H HOCNH    H  C.sub.3 H.sub.6 NHCOH                                                                      Blue                                          129    H CH.sub.3 OCNH                                                                           H  C.sub.3 H.sub.6 NHCOCH.sub.3                                                               Blue                                          130    Cl                                                                               CH.sub.3 OCNH                                                                           H  C.sub.3 H.sub.6 NHCOCH.sub.3                                                               Blue                                          131    H CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.4 CN                                                                         Violet                                        132    Cl                                                                               CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.4 CN                                                                         Blue                                          133    H CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.4 OH                                                                         Blue                                          134    Cl                                                                               CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.4 OH                                                                         Blue                                          135    H CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                          Violet                                        136    Cl                                                                               CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                          Blue                                          137    H CH.sub.3 CONH                                                                           H  C.sub.3 H.sub.6 SO.sub.2 CH.sub.3                                                          Blue                                          138    H CH.sub.3 CONH                                                                           CH.sub.3                                                                          C.sub.2 H.sub.5                                                                            Blue                                          139    Cl                                                                               CH.sub.3 CONH                                                                           CH.sub.3                                                                          C.sub.2 H.sub.5                                                                            Blue                                          140    H CH.sub.3 CONH                                                                           H  C.sub.3 H.sub.6 NHCOCH.sub.2 OH                                                            Blue                                          141    Cl                                                                               CH.sub.3 CONH                                                                           H  C.sub.3 H.sub.6 NHCOCH.sub.2 OH                                                            Blue                                          142    H (CH.sub.3).sub.2 CHCONH                                                                 H  C.sub.3 H.sub.6 NHCOCH(CH.sub.3).sub.2                                                     Blue                                          143    H CH.sub.3 CH.sub.3                                                                          C.sub.3 H.sub.6 NHCOH                                                                      Violet                                        144    Cl                                                                               CH.sub.3 CH.sub.3                                                                          C.sub.3 H.sub.6 NHCOH                                                                      Violet                                        145    H CH.sub.3 CH.sub.3                                                                          C.sub.2 H.sub.5 NHCOH                                                                      Violet                                        146    Cl                                                                               CH.sub.3 CH.sub.3                                                                          C.sub.2 H.sub.5 NHCOH                                                                      Violet                                        147    H CH.sub.3 CONH                                                                           H  C.sub.3 H.sub.7 NHCOH                                                                      Blue                                          148    H CH.sub.3 CONH                                                                           H  C.sub.2 H.sub.5                                                                            Blue                                          __________________________________________________________________________

The synthetic polyamide fibers which can be dyed with the novel azo compounds are well known and have a basis of a linear polyamide such as nylon 66 (polyhexamethylene adipamide) manufactured by the polymerization of adipic acid and hexamethylenediamine, nylon 6 (polycaprolactum) prepared from epsilon-aminocaproic acid lactum (caprolactum) and nylon 8. A detailed description of the synthetic polyamide materials which are dyed bright, fast shades by the compounds of the invention is set forth in U.S. Pat. No. 3,100,134. Although our novel compounds are particularly valuable dyes for polyamide fibers, they also can be used to dye cellulose acetate and polyester fibers fast reddish-blue to blue shades. Our compounds can be converted to the corresponding cationic azo compounds by treating the former with an alkylating agent such as dimethyl sulfate which results in alkylation of the benzisothiazolyl nitrogen atom. Such cationic compounds are useful for dyeing acrylic, modacrylic and sulfonate-modified polyester and polyamide fibers.

Although the invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A compound having the formula ##STR10## wherein R¹ and R² each is hydrogen, lower alkyl, lower alkoxy, chloro or bromo and A is ##STR11## wherein R³ is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, lower alkanoylamino, or lower alkoxycarbonylamino;R⁴ is hydrogen; R⁵ is hydrogen, lower alkyl or when R³, R⁶ and R⁷ each is methyl, R⁵ methyl; R⁶, r⁷ and R⁹ each is hydrogen or R⁶ and R₇ each is methyl; and R⁸ is lower alkyl or lower alkyl substituted with hydroxy, sulfonamido, lower alkylsulfonamido, lower dialkylsulfonamido, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, acetamido, hydroxy substituted lower alkanoylamino, lower alkanoyloxy, or lower alkoxycarbonyl.
 2. A compound having the formula ##STR12## wherein R¹ is hydrogen, chloro or bromo positioned at the 5 or 6 position;R³ is methyl, lower alkoxycarbonylamino or lower alkanoylamino; R⁵ is hydrogen or lower alkyl; and R⁸ is lower alkyl substituted with sulfonamido, lower alkylsulfonamido, lower dialkylsulfonamido, hydroxy substituted lower alkanoylamino; lower alkyl; hydroxyethyl; hydroxypropyl; lower alkoxyethyl; lower alkoxypropyl; carbamoylethyl; lower alkylcarbamoylethyl; lower alkanoylaminoethyl; lower alkanoylaminopropyl; lower alkoxycarbonlaminoethyl; lower alkoxycarbonylaminopropyl; lower alkylsulfonamidoethyl or lower alkylsulfonamidopropyl.
 3. A compound according to claim 1 having the formula ##STR13##
 4. A compound according to claim 1 having the formula ##STR14##
 5. A compound according to claim 1 having the formula ##STR15##
 6. A compound according to claim 1 having the formula ##STR16##
 7. A compound according to claim 1 having the formula ##STR17## 